EP1466664B1 - Verwendung eines bimetallkatalysators zur behandlung von nitrathaltigem wasser - Google Patents

Verwendung eines bimetallkatalysators zur behandlung von nitrathaltigem wasser Download PDF

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Publication number
EP1466664B1
EP1466664B1 EP02740773A EP02740773A EP1466664B1 EP 1466664 B1 EP1466664 B1 EP 1466664B1 EP 02740773 A EP02740773 A EP 02740773A EP 02740773 A EP02740773 A EP 02740773A EP 1466664 B1 EP1466664 B1 EP 1466664B1
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Prior art keywords
catalyst
noble metal
hydrotalcite
accordance
nitrates
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Expired - Lifetime
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EP02740773A
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English (en)
French (fr)
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EP1466664A1 (de
Inventor
Avelino Inst. de Tecnologia Quimica Corma Canos
Antonio Inst. de Tecno. Quimica PALOMARES GIMENO
José Gregorio Inst. de Tecno.Quimica PRATO MORENO
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Consejo Superior de Investigaciones Cientificas CSIC
Universidad Politecnica de Valencia
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Consejo Superior de Investigaciones Cientificas CSIC
Universidad Politecnica de Valencia
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/70—Treatment of water, waste water, or sewage by reduction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/005—Spinels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/007—Mixed salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8926—Copper and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0205—Impregnation in several steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C02F2101/163—Nitrates
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C02F2101/166—Nitrites
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen

Definitions

  • the present invention belongs to the field of use of catalysts, particularly that of bimetallic catalysts, in the purification of natural waters by means of catalytic elimination of nitrates and nitrites that are present.
  • Nitrates are stable ions highly soluble in water, which can be eliminated by physical/chemical treatments such as ion exchange, reverse osmosis and electrodialysis. Nevertheless, these techniques end up by generating a concentrated solution of these ions and it is therefore necessary to employ other techniques that are more respectful of the environment [ A, Kapoor and T. Viraraghavan, J., Environ. Eng., 123 (4), 371 (1997 )].
  • Porous support selected from among aluminumoxide, silicumoxiden, aluminosilicates and active carbon impregnated by a metallic component, have been described in EP-A-0359074 for eliminating nitrates and nitrites from water.
  • Hydrotalcite supports in different catalysts have been described for different reactions, for example dehydrogenation ( WO-00/38832 , WO-99/46039 ), preparing aromatic compounds ( EP-0476489 ) but never for eliminating nitrates from water as described in the present invention.
  • the present invention aims to overcome the drawbacks of conventional treatments of waters containing nitrates by means of a catalyst for the reduction of nitrates in waters in which it has been surprisingly seen that a support with an Mg/Al structure and especially with a hydrotalcite structure in the formulation of the overall catalyst produces a catalyst that is very active, selective and stable.
  • the present invention refers to the use of a bimetallic catalyst in a process for eliminating nitrates in liquid phase, preferably for the treatment of waters containing nitrates, which comprises a support and at least one noble metal and at least one non-noble metal, the catalyst, in elemental and anhydrous form, having a composition corresponding to the formula: XYMgAl, in which X is at least one noble metal, preferably selected among Pd, Pt, Ru, Ir and Rh; Y is at least one non-noble metal, preferably selected among Cu, Sn, Zn, In, Ni, Ag, Fe or Co, Mg is magnesium, Al is aluminium.
  • Mg and Al preferably form a hydrotalcite structure.
  • the metals can have been incorporated into the hydrotalcite structure by impregnation or during the synthesis stage of the hydrotalcite.
  • non-noble metal or metals can have been incorporated into the hydrotalcite structure during the synthesis stage of the hydrotalcite, in which case the noble metal or metals have been incorporated by impregnation in a stage subsequent to the synthesis stage.
  • Mg and Al are present in the form of aluminium and magnesium oxides obtained from a precursor of hydrotalcite by calcination in air at temperatures between 350 and 800 °C, for a period of between 1 and 20 hours.
  • at least one noble metal and at least one non-noble metal can have been incorporated into the structure of the hydrotalcite precursor during the synthesis stage of the hydrotalcite.
  • the non-noble metal or metals have been incorporated into the structure of the precursor during the synthesis stage of the hydrotalcite in order to form oxides of Mg/Al/non-noble metal, in which case the noble metal or metals have been incorporated by impregnation in a stage subsequent to the synthesis stage.
  • the use of the catalyst of the present invention is for water treatment processes wherein the nitrates are eliminated in the liquid phase, and which consist of reducing the nitrates to nitrogen using a reducing agent, such as might be for example hydrogen, formic acid, hydrocarbons and combinations thereof.
  • a reducing agent such as might be for example hydrogen, formic acid, hydrocarbons and combinations thereof.
  • the hydrotalcite consists of a laminar structure that can be considered to derive from that of brucite, Mg(OH) 2 , wherein some of the magnesium atoms octahedrally coordinated by OH groups and which form an infinite two-dimensional lamina, have been replaced with trivalent metals (in this case, Al 3+ ), thereby generating an excess of positive charge in the lamina which has to be compensated with anions (normally, CO 3 2- ) which are located in the interlaminar space.
  • the laminas are stacked one on top of another, giving rise to a laminar structure for these compounds.
  • Hydrotalcite can be prepared by, for example, coprecipitation of a solution containing the appropriate metals in the form of soluble salts, preferably aluminium nitrates and magnesium nitrate, with an alkaline solution formed by a mixture of hydroxides and alkaline carbonates, preferably NaOH and Na 2 CO 3 , in sufficient concentration for achieving total precipitation of the metals of the first solution.
  • the two solutions are mixed vigorously.
  • the resulting gels are aged for between 3 and 20 hours at a temperature between 20 and 250 °C.
  • the products are filtered and washed until the filtrate has a pH between 6.8 and 7.5. Finally, the product is calcined at a temperature above 300 °C.
  • the noble metal preferably Pd, Pt, Ru, Ir or Rh
  • the non-noble metal preferably Cu, Sn, Zn, In, Ni, Fe, Ag or Co
  • the noble metal preferably Pd, Pt, Ru, Ir or Rh
  • the non-noble metal preferably Cu, Sn, Zn, In, Ni, Fe, Ag or Co
  • the percentage of noble metal oxide with respect to the mixture obtained is between 0.1 and 30 % by weight, preferably between 0.5 and 15 % by weight.
  • the preferred percentage of non-noble metal lies in the range 0.05 % to 10 % by weight.
  • One or two metals can also be incorporated into the hydrotalcite by adding a soluble salt of the metal to the solution that contained the Mg and Al salts during the synthesis stage.
  • concentrations are adjusted in order to obtain the desired proportions of metals in the final catalyst.
  • a copper compound such as for example copper nitrate
  • the necessary amount of a copper compound is added to the solution of aluminium nitrate and magnesium nitrate in order to obtain the quantity of copper that is desired in the final product.
  • the synthesised hydrotalcite or preferably hydrotalcite synthesised at a temperature between 350 and 800 °C for a period of between 1 and 20 hours, or more preferably hydrotalcite calcined at between 400 and 600 °C for a period of between 1 and 12 hours, can be used as support.
  • the calcination is carried out in the presence of air and preferably in the absence of CO 2 .
  • the second metal can be incorporated by impregnation on the hydrotalcite structure or preferably on the structure resulting from calcining the synthesis hydrotalcite according to the calcination conditions stated above.
  • the resulting material can be used as a catalyst or preferably calcined according to the conditions described above before being used as a catalyst.
  • the material is suitable for the treatment of waters containing nitrates and nitrites, in particular for eliminating nitrates present in natural waters.
  • a reducing agent preferably hydrogen or a source of hydrogen, such as for example hydrocarbons dissolved in nitrogen
  • the catalyst reduces the nitrates to nitrogen, forming a minimum quantity of ammonia.
  • 850 ml of an aqueous solution (A) of Mg(NO 3 ) 2 and Al(NO 3 ) 3 , 1.125 M in Mg(II) and 0.375 M in Al (III), and an aqueous solution (B): 3.375 M of NaOH and 1 M of Na 2 CO 3 are prepared.
  • the two solutions are mixed while being vigorously stirred and the pH is kept at 13.
  • the precipitate is then left to age for 18 h at 80 °C and it is filtered and washed until the pH of the wash waters is 7.
  • the sample obtained is calcined at 750 °C, with the BET area being 178 m 2 .g -1 .
  • the necessary quantity of copper is then impregnated at pore volume in order to 1.5 % by weight of copper.
  • the impregnated material is then dried and calcined at 500 °C.
  • the necessary quantity of palladium is then impregnated at pore volume in order to 5 % by weight of palladium. It is then dried and calcined at 500 °C.
  • a catalyst is prepared starting from a solution (A): 1.2 M in Mg(II) and 0.3 M in Al (III), and an aqueous solution (B): 3.33 M of NaOH and 1 M of Na 2 CO 3 are prepared.
  • the two solutions are mixed while being vigorously stirred and the pH is kept at 13.
  • the precipitate is then left to age for 18 h at 80 °C and it is filtered and washed until the pH of the wash waters is 7.
  • the sample obtained is calcined at 750 °C, with the BET area being 170 m 2 .g -1 and the copper content being 1.5 % weight.
  • the necessary quantity of palladium is then impregnated at pore volume in order to 5 % by weight of palladium.
  • the impregnated material is dried and calcined at 500 °C.
  • the catalyst of example 1 is used in order to evaluate its capacity for elimination of nitrates.
  • the material is first reduced in a flow of hydrogen at 500 °C for 2 hours and then hydrogenated in the liquid phase for 60 minutes at ambient temperature.
  • 0.8 g of catalyst is used in order to try to eliminate the nitrates present in 600 ml of a solution with a nitrates concentration of 90 mg/l.
  • the reaction is left to take place for 2 hours and the evolution of the concentration of nitrates, nitrites and NH 4 + during the reaction can be seen in figures 2 and 3.
  • the catalyst of example 2 is used in order to evaluate its capacity for elimination of nitrates following the same process as that described in example 4 and with the results shown in Figures 1, 2 and 3 being observed.
  • the catalyst of example 3 is used in order to evaluate its capacity for elimination of nitrates following the same process as that described in example 4 and with the results obtained in Figures 1, 2 and 3 being observed.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Catalysts (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Claims (16)

  1. Verwendung eines Katalysators umfassend einen Träger und wenigstens ein Edelmetall und wenigstens ein unedles Metall, wobei der Katalysator, in elementarer und wasserfreier Form eine Zusammensetzung aufweist, entsprechend der Formel

            XYMgAl

    wobei X wenigstens ein Edelmetall ist;
    Y wenigstens ein unedles Metall ist;
    Mg Magnesium ist;
    Al Aluminium ist;
    in einem Verfahren zum Beseitigen von Nitraten aus einer flüssigen Phase.
  2. Verwendung eines Katalysators gemäß Anspruch 1, dadurch gekennzeichnet, dass Mg und Al eine Hydrotalcitstruktur bilden.
  3. Verwendung eines Katalysators gemäß Anspruch 1, dadurch gekennzeichnet, dass das Edelmetall gewählt wird aus Pd, Pt, Ru, Ir und Rh.
  4. Verwendung eines Katalysators gemäß Anspruch 1 oder 3, dadurch gekennzeichnet, dass das Edelmetall in der Form von Edelmetalloxid vorhanden ist, in einem Verhältnis Bezug nehmend auf das Gesamtgewicht des Katalysators von 0,1 bis 30 Gew.-%, vorzugsweise 0,5 bis 15 Gew.-%.
  5. Verwendung eines Katalysators gemäß Anspruch 1, 3 oder 4, dadurch gekennzeichnet, dass das Edelmetall Pd ist.
  6. Verwendung eines Katalysators gemäß Anspruch 1, dadurch gekennzeichnet, dass das unedle Metall gewählt wird aus Cu, Sn, Zn, In, Ni, Ag, Fe oder Co.
  7. Verwendung eines Katalysators gemäß Anspruch 1 oder 6, dadurch gekennzeichnet, dass das unedle Metall in der Form eines Oxids eines unedlen Metalls vorhanden ist, in einem Verhältnis Bezug nehmend auf das Gesamtgewicht des Katalysators von 0,5 bis 10 Gew.-%.
  8. Verwendung eines Katalysators gemäß Anspruch 1, 6 oder 7, dadurch gekennzeichnet, dass das unedle Metall Cu ist.
  9. Verwendung eines Katalysators gemäß Anspruch 2, dadurch gekennzeichnet, dass die Metalle in die Hydrotalcitstruktur durch Tränken eingeführt werden.
  10. Verwendung eines Katalysators gemäß Anspruch 2, dadurch gekennzeichnet, dass die Metalle in die Hydrotalcitstruktur während der Synthesestufe des Hydtrotalzits eingeführt werden.
  11. Verwendung eines Katalysators gemäß Anspruch 2, dadurch gekennzeichnet, dass wenigstens ein unedles Metall während der Synthesestufe des Hydrotalcits in die Hydrotalcitstruktur eingeführt wird und dass wenigstens ein Edelmetall durch Tränken in einer Stufe eingeführt wird, welche auf die Synthesestufe folgt.
  12. Verwendung eines Katalysators gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, dass Mg und Al in der Form von Aluminium- und Magnesiumoxiden vorhanden sind, beginnend mit einem Vorläufer von Hydrotalcit durch Calcinieren in Luft bei Temperaturen zwischen 350 und 800°C, über einen Zeitraum von zwischen 1 und 20 Stunden.
  13. Verwendung eines Katalysators gemäß Anspruch 12, dadurch gekennzeichnet, dass wenigstens ein Edelmetall und wenigstens ein unedles Metall während der Synthesestufe in die Struktur des Hydrotalcitvorläufers des Hydrotalcits eingeführt wird.
  14. Verwendung eines Katalysators nach Anspruch 13, dadurch gekennzeichnet, dass ein unedles Metall oder Metalle in die Struktur des Vorläufers während der Synthesestufe des Hydrotalcits eingeführt werden, um Oxide von Mg/Al/unedlem Metall zu bilden, und dass wenigstens ein Edelmetall durch Tränken in einer Stufe eingeführt wurde, welche auf die Synthesestufe folgt.
  15. Verwendung eines Katalysators gemäß einem der Ansprüche 1 bis 14, dadurch gekennzeichnet, dass sie das Reduzieren der Nitrate zu Stickstoff unter Verwendung eines Reduktionsmittels umfasst.
  16. Verwendung eines Katalysators gemäß Anspruch 15, dadurch gekennzeichnet, dass das Reduktionsmittel gewählt wird unter Wasserstoff, Forminsäure, Kohlenwasserstoffe und Kombinationen dieser.
EP02740773A 2001-06-15 2002-06-14 Verwendung eines bimetallkatalysators zur behandlung von nitrathaltigem wasser Expired - Lifetime EP1466664B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
ES200101471A ES2186547B1 (es) 2001-06-15 2001-06-15 Un catalizador bimetalico para el tratamiento de aguas que contienen nitratos.
ES200101471P 2001-06-15
PCT/ES2002/000296 WO2002102507A1 (es) 2001-06-15 2002-06-14 Un catalizador bimetalico para el tratamiento de aguas que contienen nitratos

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Publication Number Publication Date
EP1466664A1 EP1466664A1 (de) 2004-10-13
EP1466664B1 true EP1466664B1 (de) 2007-09-26

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US (2) US20040164028A1 (de)
EP (1) EP1466664B1 (de)
JP (1) JP2004528982A (de)
AT (1) ATE374076T1 (de)
DE (1) DE60222700T2 (de)
DK (1) DK1466664T3 (de)
ES (2) ES2186547B1 (de)
PT (1) PT1466664E (de)
WO (1) WO2002102507A1 (de)

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CN103570114B (zh) * 2013-10-24 2015-03-25 上海大学 一种还原处理水中硝酸盐的方法
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JP2004528982A (ja) 2004-09-24
ES2294139T3 (es) 2008-04-01
US7857981B2 (en) 2010-12-28
WO2002102507A1 (es) 2002-12-27
PT1466664E (pt) 2007-12-27
US20080302736A1 (en) 2008-12-11
ES2186547A1 (es) 2003-05-01
EP1466664A1 (de) 2004-10-13
ES2186547B1 (es) 2004-08-01
DE60222700D1 (de) 2007-11-08
US20040164028A1 (en) 2004-08-26
DE60222700T2 (de) 2008-07-17
ATE374076T1 (de) 2007-10-15
DK1466664T3 (da) 2008-01-14

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